Azo dyes.



' UNITED STATES PATENT OFFICE.

ARTHUR ZART, OF OPLADEN. AND HUGO SCHWEITZER, 0F LEVER-KUSEN. NEAR COLOGNE, GERMANY. ASSIGNORS T0 SYNTHETIC PATENTS 00.. INC.v OF NEW YORK, N. Y., A CORPORATION OF NEW YORK.

Azo DYES.

No Drawing.

To all whom it may concern.

Be it known that we, ARTHUR Zion and HUGO Scnwnrrznn, doctors of philosophy,

n 1 chemists, cltizcns ot the (Ierman pire, residing at ()pladen and LGVQllCllSGIlM near Cologne'on-the-Rhine, Germany, have invented new and useful Improvements in Azo Dyes, of which the following is a speci fication.

\Ve have found that new and valuable azo dyestuffs can be obtained by coupling the diazo compounds of diaminosultonic= acids 6. g. para-phenylencdiamin sullouic acid which contain in one or both amino groups a nitroarylacn'lyl group or an acidylaminoarylacldyl group e. 5

l NO: NH

I come with p-yrazolone compoimds which can be obtained from aminothiazole compoumls by condensing their hydrazins with acetoacetic ester, etc., reducing the nitro group or splitting oil' the acidyl radical by saponilication.

The new products are after being dried and pulverized in the shape of their alkaline salts generally yellowish powders soluble in SOaH soluble in Water with a yellow coloration, yielding upon reduction with stannous chlorid and hydrochloric acid meta-amino- Patented ()et. 27, .1914.

water. Upon reduction with chlorid and hydrochloric acid they are broken up into an aromatic diaminosul'ionic i acid substituted by an aminoar \'lacidyl radii cal and an aminopyrazolone compound des lrived from an aromatic thiazole product 1 and substituted by the radical of such thii azole product. They dye cotton in yellowish shades, which by diazotation-aml dei-velopment on fiber with beta-naphthol are l converted into reddish-yellow shades fast to washing.

l nv order to illustrate the new process more fully the following example is given. the parts beimg by weight: 313T parts of meta nitrohenzoyl para phenylenediamin sull onic acid are diazotixed with parts of sodium nitrite and lrvdrochlorie acid and the diazotized derivative is combined with 101 parts ol 1-(h hydrothiotolyl2-1nethyl-5- pyrazolone sullonic acid dissolved in a solution of sodium carbonate. o parts of crystalline sodium sullid are added to it. Subsequently the mixture is boiled up and the dyestull is salted out with common salt, liltcred oil and dried. It dyes cotton a vellowish shade which on development with beta-naphthol changes into a reddish-yellow Fast to washing.

The new dyestutl' is in the shape of its sodium salt a yellow powder having in a l free state most probably the formula:

o-on, on

l zoyl ll diaminodiphcnylurea 3.3 disull tonic acid, l-para-nitn1-benzoyl':l-.-l'-din minostilbenedisultonic acid. -lmetanitrobenzoyl-l.-t-diaminodiphcnyl-3.3disulfonic acid, 1-nieta'-nitrobenzoyl-meta-aminobcn zoyl-1.-l-phenylenediamin 3 sul'l'onic acid, inono-meta-nitrobenzoyl-1.5-naphthylenediamin-il-snl'fonic acid, pyrazolone from the stannous hydrazin of primulin sulfonic acid and aceto l acetic ester, 1 dehydrothiotolyl-S-pyrazolone-tt-carboxylic acid, pyrazolone obtained and from the hydrazin of the para-aminophenyl- 1.2 naphthothiazole I sulfonic acid and aceto-acetic ester.

We claim:

1. The new azo dyestutls which are after being dried and pulverized in the shape of their alkaline salts yellowish powders soluble in water, yielding upon reduction with stannous chlol'id and hydrochloric acid an aromatic diaminosulfonic acid substituted by an aminoaryl-acidyl radical and an. aminopyrazolone compound substituted by an aromatic thiazole radical; dyeing cotton in yellowish shades which can be converted by diazotation and by development with betanaphthol into reddish-yellow shades fast to washing, substantially as described.

2. The new azo dyestulis which are after being dried and pulverized in the shape of their alkaline salts yellowish powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid a phenylenediamin sulit'onic acid substitute'd by an aminoarylacidyl radical and an aminopyrazolone compound substituted by an aromatic thiazole radical; dyeing cottonin yellowish shades which can be converted by diazotation and by development with betauiaplithol into reddish-yel10w shades fast to washing, substantially as described.

3. The new azo dyestuffs which are after being dried and pulverized. in the shape of their alkaline salts yellowish powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid a para-phenylenediamin suli onic acid substituted by an aminoarylacidyl radical and an aminopyrazolone compound substituted by an aromatic thiazole radical; dyeing cotton in. yellowish shades which can be converted by diazotation and by development with. beta-naphthol into reddish-yellow shades fast to washing, substantially as described.

4-. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts yellowish powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid an aromatic diamino sulfonic acid substituted by an aminobenzoyl radical and an aminopyrazolone compound substituted by an aromatic tbiazole radical; dyeing cotton in yellowish shades which can be converted by diazotatlon and by development with betanaphthol into reddish-yellow shades fast to matic thiazole radical; dyeing cotton in yellowish shades which can be converted by diazotation and by development with betanaphthol into reddislryellow shades fast to washing, substantially as. described.

6. The new azo dyestuffs which are after being dried and pulverized'in the shape of their alkaline salts yellowish powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid a para-phcnylenediamin sulfonic acid substituted by an amino-benzoyl radical and an aminopyrazolone compound substituted by an aromatic thiazole radical; dyeing" cotton in yellowish shades which can be converted by diazotation and by development with beta-naphthol into reddish-yellow shades fast to washing, substantially as described.

7 The new azo dyestufis which are after being dried and pulverized in the shape of their alkaline salts yellowish powders soluble in water, yielding upon reduction with 'stannous chlorid and hydrochloric acid an by an aminoarylacidyl radical and a 4- aminopyrazolone compound substituted in l-position by an aromatic thiazole radical; dyeing cotton in yellowish shades which can be converted by diazotation and by develop ment with beta-naphthol into reddislvyellow shades fast to washing, substantially as described.

9. The new azo dyestuffs which are after being dried and pulverized in the shape of their alkaline salts yellowish powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid. a phenylenediamin sulfonic acid substituted by an aminoarylacidyl radical and a laminopyrazolone compound substituted in 1-- position by an aromatic thiazole radical;

dyeing cotton'in yellowish shadeswhich'can be converted by diazotation and by develop ment with beta-naphthol into reddish-yellow shades fast to washing, substantially as de' scribed.

10. The new azo dyestufis which are aitter being dried and pulverized in the shape of their alkaline salts yellowish powders soluble in water, yielding upon reduction with stannous chlorid and hydrochloric acid a para-phenylenediamin sultonic acid substible in water, yielding upon reduction with stannous chlorid and hydrochloric acid a a seam which is after being dried and pulverized a yellow powder soluble in Water with a yellow coloration; yielding upon reduction with stannous chlorid and hydrochloric acid meta aminobenzoyl para-phenylencdiamin sulfonic acid, l-dehydrothiotolyl-3-methyl-4 amino-S-pyrazolone sulfonic acid; dyeing cotton a yellow which can be developed with beta-naphthol into a reddish-yellow shade, substantially as described.

M 00911:! of this patent may be obtained for five cents each, by addressing the phenylenediamin sulfonic acid substituted by an aminobenzoyl radical and a fie-aminopyrazolone compound substituted in l-position by an aromatic converted bydiazotation and by development with beta-naphthol into reddish-yellow shades fast to washing, substantially as described.

12. The new azo dyestuff having in the shape of its sodium salt most probably the formula:

some NH:

In testimony whereof We have hereunto set our hands in the presence of two sub- SCIlblIlg Witnesses.

ARTHUR ZART. HUGO SCHWEITZER.

Witnesses Go'rrramn RowHNcnovEN, Rumour POLDENVALE.

"Qommlssloncr of Intent Washington, D. C.

thiazole radical; dyeing cotton in yellowish shades which can be' 

